Upgrade of the Marathon Louisiana Refining Division s Wastewater Treatment Plant to a State-of-the-Art Nitrification-Denitrification Facility Presented to Air & Waste Management Association Louisiana Section November 19, 2008 by Carl E. Adams, Jr., PhD, P.E. ENVIRON International Corporation
Presentation Outline Background and Pre-Upgrade Facilities Upgrade Design and Implementation Performance Recent Developments e e
Background and Pre-Upgrade Facilities Refinery and wastewater treatment plant (WWTP) began operation in 1976 Originally two treatment trains Third activated sludge train added in 1983 Conventional systems with External Secondary Clarifiers Past and planned expansions raised concern for capacity of existing WWTP and desire for cost-effective application of state- of-the-art technology Regulatory concern regarding potential future nitrogen discharge limits 250,000 bbls/day rated crude capacity in 2000
Background and Pre-Upgrade Facilities ENVIRON retained by Marathon in 2000 to review WWTP operations and assist in developing a wastewater Master Plan, including planning for VOC emissions and sludge residues 2001 Flows and Loads 2,100 gpm design average dry-weather flow 700 mg/l design average COD (17,900 lbs/day) 40 mg/l design average TKN (1,025 lbs/day) Projected Flows and Loads 2,310 gpm design average flow 21,640 lbs/day COD 1,250 lbs/day TKN
Background and Pre-Upgrade Facilities Pre-Upgrade Wastewater Facilities API Equalization Stormwater diversion Dissolved air flotation ti (DAF) Two treatment trains Cooling Tower Conventional Activated Sludge, i.e., external clarifier Three treatment trains (East / Middle / West) Effluent (Firewater) Pond Sludge Handling (aerobic digestion, centrifugation)
Background and Pre-upgrade Facilities AERATION TANKS SECONDARY CLARIFIERS EAST DAF WET WELL HOT WATER BYPASS RAS FLOC DAF COOLING TOWER C.T. WET WELL MIDDLE FIRE POND TANK DAF NORMAL BYPASS RAS WEST RAS CAT SETTLING POND TK 100-2 SERVES AS MAIN ONLINE EQ TANK DISCHARGES TO BIOPLANT CHARGE PUMP TK 100-3 SERVES TK AS 103 ONLINE DIVERSION/EQ 100,000 bbl TANK Floating Roof DISCHARGES TO TK 102 SUPERNATENT AEROBIC DIGESTER INFLUENT API API GRAVITY ONLY POLYMER REFINERY WASTEWATER CENTRATE TK 25-1 STORMWATER DIVERSION TK 100-4 STORMWATER DVIERSION DISCHARGES BACK TO API TK 100-5 PINNACLE RUNDOWN TANK (POLYMER REFINERY) DISCHARGES TO API BIOSLUDGE DISPOSAL TO THERMAL DESORBER
Background and Pre-Upgrade Facilities Pre-Upgrade Performance Hydraulic capacity Limited to 2,700 gpm maximum throughput Projected future max flow of up to 3,500 gpm Marginal DAF performance Hydraulic limited Marginal activated sludge performance Organic overload Limited aeration capacity no standby facilities High operating temperatures
Background and Pre-Upgrade Facilities ENVIRON recommendations (2001) Provide additional flotation train Activated sludge system (near term) Increase MLSS/MLVSS (i.e., lower F/M) Add standby aeration capacity Decrease aeration basin temperatures Activated sludge system (long term) Add additional bioreactor aeration and clarifier capacity Design for nitrogen removal (nitrification-denitrification) Limited footprint consider state-of-the-art integral clarifier system
Upgrade Design and Implementation 2002 ENVIRON Feasibility Study Feasibility level l design and cost estimates t for new fourth treatment t t train New fourth train to include Induced Gas Flotation Closed Circuit Cooling Tower Activated sludge with nitrification-denitrification ADVENT Integral System (AIS) technology
Conventional System Aspects Influent Wastewater CENTRAL MOTOR/GEAR DRIVE MECHANISM AEROBIC BASIN Treated Effluent SECONDARY CLARIFIER STRUCTURAL SHELL SLUDGE SCRAPPER MECHANISM Conventional clarifier has capital and operating constraints... Return Activated Sludge SLUDGE RETURN PUMPS Concrete or steel structural shell to hold 3-5 m of water. Internal sludge raking mechanism. Sludge return pumps and piping. Aeration Basins Clarifiers LARGE FOOTPRINT
What is The ADVENT Integral System (AIS)? Basically, a Cost-Efficient Reconfiguration of the Conventional Activated Sludge Process
AIS Components Patented Induced Downward Velocity allows higher concentrations of MLSS. System MLSS, mg/l Conventional Activated Sludge 2,000 to 4,000 AIS 6,000 to 8,000 3 1. Influent 5 5 2. Mixed Liquor Inlet to Airlift Pump 3. Deaeration / Transition / Flocculation Effluent (DTF) to Clarifier 4 4. Center Well Discharge 2 5. Effluent over Weir & to Final Discharge 8 1 6 7 6. Thickened MLSS Return to Aeration Basin 7. Aeration Current to Remove MLSS from Clarifier 8. Waste Excess Biomass
DTF Components TRANSITION CHANNEL FLOCCULATION AIR LIFT PUMP DEAERATION CHAMBER DART VALVE FOR VARIABLE LEVEL CONTROL FOAM SKIMMING AND FLOCCULATION ENHANCEMENT DTF system components enhance coagulation and flocculation of biomass particles Each DTF is configured and calibrated to maintain maximum degassing/biomass flocculation Excellent removal of surfactant, oils and foaming materials before clarifier. Can integrate polishing chemical treatment for PO 4, heavy metals, F -, etc. The DTF is designed ed to be operator-free ee with minimal or no maintenance. CLARIFIER TRANSITION CHANNEL
The First AIS System (1993)- CIRCULAR Configuration... GE Plastics Grangemouth, Scotland
The AIS System - System Configurations The five most common configurations are... Rectangular Peripheral Internal Pyramidal Circular Square
Upgrade Design and Implementation Biological Treatment Chemistry Organic Removal Biological Oxidation of Organics (e.g., Hydrocarbons, Phenols) to Carbon Dioxide and Water: C 6 H 5 OH + 7O 2 6CO 2 + 3H 2 O + new bacteria Nitrification Biological Oxidation of Ammonia to Nitrate: NH 4+ + 2O 2 + 2HCO 3 - NO 3- + H 2 0 + 2H 2 CO 3 + new bacteria Denitrification Biological Oxidation of Organics and Conversion of Nitrate to Nitrogen Gas: NO 3- +0.83CH 3 OH + 0.17H 2 CO 3 0.5N 2 +1.33H 2 0 + HCO 3- + new bacteria HETEROTROPHS AUTOTROPHS Strict aerobes, must have D.O. Aerobic w/d.o. Anoxic w/no D.O. but NO 3
Upgrade Design and Implementation Conventional Nitrification-Denitrification A Typical Nitrifying-Denitrifying Activated Sludge System... Influent Aerobic Basin Secondary Clarifier Treated Effluent Anoxic Basin Nitrate Recycle Return Activated Sludge
Upgrade Design and Implementation AIS Nitrification-Denitrification Control Valve X Nitrated Recycle Influent Wastewater AIR LIFT PUMP AEROBIC BASIN Treated Effluent AIS INTEGRAL CLARIFIER ANOXIC BASIN Denitrified Water (Gravity Flow)
First Major AIS Nitrification-Denitrification System NH 4 -N = 4,000 mg/l Clarification Aerobic Zone Influent Jet Mixing Anoxic Zone United States Steel Coke Plant, Gary, Indiana
Upgrade Design and Implementation AIS Flow Path
Modular Ring Configuration PERIPHERAL ANOXIC & CENTRAL AEROBIC ZONES MODULAR RING CLARIFIER PERIPHERAL ANOXIC ZONE CENTRAL AEROBIC ZONE DTF CLARIFIER FEED STRUCTURE WALKWAYS & WEIRS
Minor Off-Gas Off-Gas Pretreated Influent Mixer Recycle for Nitrate Removal Air Lift Pump Treated Effluent ANOXIC STAGE (Biodegradable Organics, Benzene & Nitrate Removal) Return Activated Sludge Aeration Grid AEROBIC STAGE (Biodegradable Pretreated Organics, Benzene & Influent Ammonia Removal) 1 Off-Gas Minor Off-Gas Off-Gas Blower Air 6 Integral Secondary Clarifier Integral Secondar y Clarifier 9 9 10 Treated Effluent Air Lift Pump 7 7 5 AEROBIC 2 nd STAGE (Zone 2-Series Polishing) Recycled Activated Sludge Turbine Mixer ANOXIC 1 st STAGE (Thoroughly Mixed) 2 Eight Pipe Connectors From Anoxic To Aerobic Stage 3 Recycled Activated Sludge 4 AEROBIC 2 nd STAGE (Zone 1-Thoroughly Mixed) Aeration Grid 8 8 Aeration Grid Blower Air
Upgrade Design and Implementation AIS Flow Path Marathon Oil Co. Louisiana Refining Division Garyville, LA Influent Design Second Stage: Aerobic Zone Second Stage: Aerobic Zone First Stage: Anoxic Or Aerobic Zone (Involves Turning Aeration Header One Valve) Flow = 900 gpm (design) = 1,400 gpm (max) COD = 6,000 lbs/day TKN = 485 lbs/day Effluent Design BOD 5 (s) < 15 mg/l NH 3 -N <5mg/L NO 3 -N < 6 mg/l TSS < 30 mg/l
Upgrade Design and Implementation Front End Engineering Design (FEED) in 2003 AIS Contract Awarded April 2004 Technology, Design and Startup by The ADVENT Group, Inc. (now ENVIRON) Reactor Fabrication and Construction by Matrix Service, Inc. AIS Commissioned in April 2005 Performance Test Completed July 2005
Fourth Train Construction The AIS System: Refineries Nitrification--Denitrification Nitrification Closed Circuit C li TTower Cooling MarathonAshland REFINERY Garyville, LA UNICELL Induced Air Floatation
Performance 2007 AIS Nitrogen Balance: Short Term Nitrates Are Annually Reported on Marathon s Toxic Release Inventory (TRI) Marathon and ENVIRON Executed a One Week Sampling and Analysis Effort in July 2007 to Develop a Nitrogen Balance for AIS Train One
Performance 2007 AIS Nitrogen Balance: Short Term AIS Influent Characteristics PARAMETER UNITS MONDAY TUEDAY WEDNESDAY THURSDAY FRIDAY AVERAGE FLOW gpm 1,100 1,100 1,100 1,033 1,025 1,072 COD mg/l 372 260 354 307 300 318 TKN mg/l 21 18 20 18 16 19 NH 3 -N mg/l 15 16 16 16 15 16 NO 3 -N mg/l < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 TSS mg/l 34 44 95 77 50 60 AIS Effluent Characteristics PARAMETER UNITS MONDAY TUEDAY WEDNESDAY THURSDAY FRIDAY AVERAGE FLOW gpm 1,088 1,096 1,085 977 1,017 1,052 COD (s) mg/l 40 38 43 55 43 44 TKN (s) mg/l 1.3 2.3 1.3 2.3 1.8 1.8 NH 3 -N (s) mg/l 1.3 1.0 1.0 1.8 1.2 1.3 NO 3 -N (s) mg/l 1.5 0.1 0.2 0.1 0.1 0.4 TSS mg/l 19 19 18 23 17 19
Performance 2007 AIS Nitrogen Balance: Short Term Conclusions of the Study Average Total Nitrogen Removal Efficiency During the Study was ~ 89% Denitrification in the AIS was Confirmed Presents an Opportunity for TRI Reduction Without Denitrification ~ 87 tons/yr NO 3 (AIS Only, Assumes 10 mg/l Effluent NO 3 -N) With Denitrification ~ 15 tons/yr NO 3 (AIS Only, Based on 2007 Average Effluent NO 3 -N of 1.7 3 3 mg/l)
Performance: Long Term 2007 AIS Ammonia & Nitrate Concentrations 35 14 2007 Avg Influent NH3-N = 16.6 mg/l 2007 Avg Effluent NH3-N = 1.2 mg/l 2007 Avg Effluent NO3-N = 1.7 mg/l 30 12 25 10 H3-N (mg/l) N 20 15 8 6 O3-N (mg/l) N 10 4 5 2 0 Jan-07 Feb-07 Apr-07 May-07 Jul-07 Sep-07 Oct-07 Dec-07 0 Effluent NH3-N Influent NH3-N Effluent NO3-N
2-Feb-06 9-Feb-06 26-Jan-06 19-Jan-06 12-Jan-06 Performance: Long Term Marathon Garyville WWTP Effluent NH3-N 3.00 2.50 200 2.00 1.50 NH3-N (mg/l) 1.00 0.50 0.00 22-Sep-05 29-Sep-05 6-Oct-05 13-Oct-05 20-Oct-05 27-Oct-05 3-Nov-05 10-Nov-05 17-Nov-05 24-Nov-05 1-Dec-05 8-Dec-05 15-Dec-05 22-Dec-05 29-Dec-05 5-Jan-06 AIS Conventional Clarifiers
9-Feb-06 2-Feb-06 26-Jan-06 Performance: Long Term Marathon Garyville WWTP Effluent TOC 40 35 30 25 20 TOC (mg/l) 15 10 5 0 22-Sep-05 29-Sep-05 6-Oct-05 13-Oct-05 20-Oct-05 27-Oct-05 3-Nov-05 10-Nov-05 17-Nov-05 24-Nov-05 1-Dec-05 8-Dec-05 15-Dec-05 22-Dec-05 29-Dec-05 5-Jan-06 12-Jan-06 19-Jan-06 AIS West Clarifier Mid Clarifier East Clarifier
2/9/2006 1/26/2006 2/2/2006 2 1/ 1/12/2006 1/19/2006 1/ 1/ Performance: Long Term Marathon Garyville WWTP Clarifier Composite Effluent COD 180 160 140 120 100 80 105 mg/l avg COD COD (mg/l) 60 40 20 0 9/22/2005 9/29/2005 10/6/2005 10/ 0/13/2005 10/ 0/20/2005 10/ 0/27/2005 11/3/2005 11/ 1/10/2005 11/ 1/17/2005 11/ 1/24/2005 12/1/2005 12/8/2005 12/ 2/15/2005 12/ 2/22/2005 12/ 2/29/2005 1/5/2006 7-day Rollling Avg Avg 24-hr Avg
2-Feb-06 9-Feb-06 26-Jan-06 Performance: Long Term Marathon Garyville WWTP Effluent Turbidity 35.00 30.00 25.00 20.00 15.00 Turbidity (NTU) 10.00 5.00 0.00 22-Sep-05 29-Sep-05 6-Oct-05 13-Oct-05 20-Oct-05 27-Oct-05 3-Nov-05 10-Nov-05 17-Nov-05 24-Nov-05 1-Dec-05 8-Dec-05 15-Dec-05 22-Dec-05 29-Dec-05 5-Jan-06 12-Jan-06 19-Jan-06 AIS West Clarifier Mid Clarifier East Clarifier
2008 Comparative Effluent Turbidity AIS Effluent Turbidity 65.0 60.0 55.0 50.0 45.0 40.0 ty (NTU) Turbidit 35.0 30.0 25.0 Three External Clarifiers One Integrated Clarifier 20.0 15.0 10.0 5.0 0.0 Mar-08 Apr-08 May-08 Jun-08 Jul-08 Aug-08 Sep-08 Oct-08 Nov-08 AIS East Clarifier Middle Clarifier West Clarifier
2008 AIS TOC Performance AIS Total Organic Carbon Removal 280 260 240 220 200 180 TOC (mg/l) 160 140 120 100 80 60 40 20 0 Mar-08 Apr-08 May-08 Jun-08 Jul-08 Aug-08 Sep-08 Oct-08 Nov-08 Influent TOC Effluent TOC
2008 AIS Effluent NO 3 -N AIS Nitrogen Removal 38 36 34 32 30 28 26 NH3-N / NO3-N (mg/l L) 24 22 20 18 16 14 12 10 8 6 4 2 0 Mar-08 Apr-08 May-08 Jun-08 Jul-08 Aug-08 Sep-08 Oct-08 Nov-08 Effluent NO3-NN Influent NH3-NN
Recent Developments Garyville Major Expansion Project 180,000 bbls/day capacity expansion at LRD New 5 th Train (AIS Train Two) under construction at WWTP Potential ti to treat t API/DGF and other WWTP VOC emissions i with AIS VOC emissions are vented through aeration blowers into coarse or fine bubble diffusers along with normal air for biotreatment Low surface area for AIS is optimum for VOC emissions modeling
VOC Off-Gas Potential From Conventional Activated with External Clarifier (High Surface Area)
VOC Off-Gas Potential From Conventional Activated with Integrated Clarifier (Low Surface Area)
Optimum Configuration for VOC Off-Gas Modeling
Authors Dr. Carl E. Adams, Jr., Global Practice Leader, Integrated Industrial Wastewater Management ENVIRON International ti Corporation cadams@environcorp.com Mr. Wally E. Dows, III; ES&S Manager Marathon Oil Company, Louisiana Refining Division wedows@marathonoil.com Mr. John Driver, Project Manager ENVIRON International Corporation jdriver@environcorp.com Mr. Chad Louque; Operations Supervisor Marathon Oil Company, Louisiana Refining Division cplouque@marathonoil.com